ABSTRACT
BACKGROUND: Chemotherapy, the mainstay treatment for metastatic cancer, presents serious side effects due to off-target exposure. In addition to the negative impact on patients' quality of life, side effects limit the dose that can be administered and thus the efficacy of the drug. Encapsulation of chemotherapeutic drugs in nanocarriers is a promising strategy to mitigate these issues. However, avoiding premature drug release from the nanocarriers and selectively targeting the tumour remains a challenge. RESULTS: In this study, we present a pioneering method for drug integration into nanoparticles known as mesoporous organosilica drugs (MODs), a distinctive variant of periodic mesoporous organosilica nanoparticles (PMOs) in which the drug is an inherent component of the silica nanoparticle structure. This groundbreaking approach involves the chemical modification of drugs to produce bis-organosilane prodrugs, which act as silica precursors for MOD synthesis. Mitoxantrone (MTO), a drug used to treat metastatic breast cancer, was selected for the development of MTO@MOD nanomedicines, which demonstrated a significant reduction in breast cancer cell viability. Several MODs with different amounts of MTO were synthesised and found to be efficient nanoplatforms for the sustained delivery of MTO after biodegradation. In addition, Fe3O4 NPs were incorporated into the MODs to generate magnetic MODs to actively target the tumour and further enhance drug efficacy. Importantly, magnetic MTO@MODs underwent a Fenton reaction, which increased cancer cell death twofold compared to non-magnetic MODs. CONCLUSIONS: A new PMO-based material, MOD nanomedicines, was synthesised using the chemotherapeutic drug MTO as a silica precursor. MTO@MOD nanomedicines demonstrated their efficacy in significantly reducing the viability of breast cancer cells. In addition, we incorporated Fe3O4 into MODs to generate magnetic MODs for active tumour targeting and enhanced drug efficacy by ROS generation. These findings pave the way for the designing of silica-based multitherapeutic nanomedicines for cancer treatment with improved drug delivery, reduced side effects and enhanced efficacy.
Subject(s)
Antineoplastic Agents , Breast Neoplasms , Cell Survival , Mitoxantrone , Organosilicon Compounds , Humans , Breast Neoplasms/drug therapy , Female , Cell Survival/drug effects , Organosilicon Compounds/chemistry , Organosilicon Compounds/pharmacology , Antineoplastic Agents/pharmacology , Antineoplastic Agents/chemistry , Antineoplastic Agents/therapeutic use , Mitoxantrone/pharmacology , Mitoxantrone/chemistry , Mitoxantrone/therapeutic use , Cell Line, Tumor , Drug Carriers/chemistry , Silicon Dioxide/chemistry , Porosity , Drug Liberation , Nanoparticles/chemistry , MCF-7 Cells , Nanomedicine/methods , Reactive Oxygen Species/metabolismABSTRACT
Periodic mesoporous organosilicas (PMOs) are high surface area organic-inorganic hybrid nanomaterials that have found broad applications in various fields of research such as in (bio)chemistry or material science. By choosing suitable organic groups in the framework of these materials, their surface properties such as polarity, optical/electrical characteristics and adsorption capacity can be tuned. This critical review provides an overview of the current state of the art in the developments and applications of some PMO nanomaterials in diverse fields of research. This is placed in the context of four leading areas of PMO nanomaterials, including chiral PMOs, plugged PMO nanomaterials, Janus PMOs and PMO-based nanomotors. The review briefly discusses the recent and key findings on these PMO nanomaterials as well as their potential applications for future developments.
Subject(s)
Nanostructures , Organosilicon Compounds , Organosilicon Compounds/chemistry , Porosity , Nanostructures/chemistry , Surface PropertiesABSTRACT
The development of a highly sensitive electrochemical sensor (E-sensor) is described based on stand-alone plastic electrodes (PE) for phosphate detection, being an essential nutrient in the marine environment. The detection mechanism is based on the chemical affinity between polyoxomolybdate anions (POM) and orthophosphate to form an electroactive phosphomolybdate complex. The custom-made E-sensor was formulated with an organic octamolybdate derivative (TBA4Mo8O26) incorporated with periodic mesoporous organosilica (PMO) to obtain a significant improvement in the analytical performances of phosphate determination. This POM@PMO combination was found to be advantageous in the determination of low concentrations of phosphate in standard solutions ranging from 1 to 500 nM, using square wave voltammetry as the detection technique. This sensitivity enhancement can be attributed to the effect of hydrophobic PMO in loading more POM moieties, owing to its highly porous structure and charged shell. Consequently, the POM@PMO-PE sensor achieved a competitive sensitivity of 4.43 ± 0.14 µA.nM-1.cm-2 and a limit of detection of 0.16 nM with good selectivity against silicates. Finally, seawater and treated wastewater samples have been tested to validate the sensor response in comparison to the official method of phosphate determination.
ABSTRACT
The current study presents a periodic mesoporous organosilica (PMO) with a high surface area and uniform-porosity material. The PMO materials were successfully synthesized and modified. The resultant material was characterized by different characterization techniques. The prepared PMO was immobilized on a stainless steel wire surface and was evaluated for headspace solid-phase microextraction of the ultra-trace amount of phthalate esters from saliva and polyethylene terephthalate containers which were in contact with hot and cold water. Separation and determination of the phthalate esters (PEs) were performed by the GC-FID and GC-MS instruments. The key parameters affecting the extraction efficiencies, including extraction temperature, extraction time, ionic strength, and desorption temperature and time, were investigated and optimized. Under optimum conditions, the repeatability for one fiber (n = 7) was 4.8-8.7%, and fiber-to-fiber reproducibility (n = 3) was 7.5-10.6% for the extracted compounds. The limits of detection of the developed method for the studied compounds were between 0.01 and 1 µg L-1. The results showed suitable coefficients of determination (R2 ≥ 0.99) for all of the analytes in the 0.05-300 µg L-1 calibration range. Acceptable recovery values of 91-107%, 82-110%, and 98-104% were obtained in saliva, polyethylene terephthalate containers hot water, and cold water, respectively.
Subject(s)
Esters , Ethane , Phthalic Acids , Reproducibility of Results , Saliva , Solid Phase Microextraction/methodsABSTRACT
(1) Background: Due to human activities, greenhouse gas (GHG) concentrations in the atmosphere are constantly rising, causing the greenhouse effect. Among GHGs, carbon dioxide (CO2) is responsible for about two-thirds of the total energy imbalance which is the origin of the increase in the Earth's temperature. (2) Methods: In this field, we describe the development of periodic mesoporous organosilica nanoparticles (PMO NPs) used to capture and store CO2 present in the atmosphere. Several types of PMO NP (bis(triethoxysilyl)ethane (BTEE) as matrix, co-condensed with trialkoxysilylated aminopyridine (py) and trialkoxysilylated bipyridine (Etbipy and iPrbipy)) were synthesized by means of the sol-gel procedure, then characterized with different techniques (DLS, TEM, FTIR, BET). A systematic evaluation of CO2 adsorption was carried out at 298 K and 273 K, at low pressure. (3) Results: The best values of CO2 adsorption were obtained with 6% bipyridine: 1.045 mmol·g-1 at 298 K and 2.26 mmol·g-1 at 273 K. (4) Conclusions: The synthetized BTEE/aminopyridine or bipyridine PMO NPs showed significant results and could be promising for carbon capture and storage (CCS) application.
Subject(s)
Carbon Dioxide , Nanoparticles , Adsorption , Aminopyridines , Humans , Porosity , TemperatureABSTRACT
BACKGROUND: There is a great interest in the efficient intracellular delivery of Cas9-sgRNA ribonucleoprotein complex (RNP) and its possible applications for in vivo CRISPR-based gene editing. In this study, a nanoporous mediated gene-editing approach has been successfully performed using a bi-functionalized aminoguanidine-PEGylated periodic mesoporous organosilica (PMO) nanoparticles (RNP@AGu@PEG1500-PMO) as a potent and biocompatible nanocarrier for RNP delivery. RESULTS: The bi-functionalized MSN-based nanomaterials have been fully characterized using electron microscopy (TEM and SEM), nitrogen adsorption measurements, thermogravimetric analysis (TGA), X-ray powder diffraction (XRD), Attenuated Total Reflectance-Fourier Transform Infrared Spectroscopy (ATR-FTIR), and dynamic light scattering (DLS). The results confirm that AGu@PEG1500-PMO can be applied for gene-editing with an efficiency of about 40% as measured by GFP gene knockdown of HT1080-GFP cells with no notable change in the morphology of the cells. CONCLUSIONS: Due to the high stability and biocompatibility, simple synthesis, and cost-effectiveness, the developed bi-functionalized PMO-based nano-network introduces a tailored nanocarrier that has remarkable potential as a promising trajectory for biomedical and RNP delivery applications.
Subject(s)
Guanidines/chemistry , Nanoparticles/chemistry , Polyethylene Glycols/chemistry , Ribonucleoproteins/chemistry , Adsorption , CRISPR-Cas Systems , Cell Survival , Cloning, Molecular , Drug Liberation , Dynamic Light Scattering , Gene Editing/methods , Polymers/chemistry , RNA, Guide, Kinetoplastida/genetics , Silanes , Streptococcus pyogenes/geneticsABSTRACT
Biodegradable periodic mesoporous organosilica (BPMO) has recently emerged as a promising type of mesoporous silica-based nanoparticle for biomedical applications. Like mesoporous silica nanoparticles (MSN), BPMO possesses a large surface area where various compounds can be attached. In this work, we attached boronophenylalanine (10BPA) to the surface and explored the potential of this nanomaterial for delivering boron-10 for use in boron neutron capture therapy (BNCT). This cancer therapy is based on the principle that the exposure of boron-10 to thermal neutron results in the release of a-particles that kill cancer cells. To attach 10BPA, the surface of BPMO was modified with diol groups which facilitated the efficient binding of 10BPA, yielding 10BPA-loaded BPMO (10BPA-BPMO). Surface modification with phosphonate was also carried out to increase the dispersibility of the nanoparticles. To investigate this nanomaterial's potential for BNCT, we first used human cancer cells and found that 10BPA-BPMO nanoparticles were efficiently taken up into the cancer cells and were localized in perinuclear regions. We then used a chicken egg tumor model, a versatile and convenient tumor model used to characterize nanomaterials. After observing significant tumor accumulation, 10BPA-BPMO injected chicken eggs were evaluated by irradiating with neutron beams. Dramatic inhibition of the tumor growth was observed. These results suggest the potential of 10BPA-BPMO as a novel boron agent for BNCT.
Subject(s)
Antineoplastic Agents/administration & dosage , Antineoplastic Agents/chemistry , Boron Compounds/chemistry , Metal Nanoparticles/administration & dosage , Neoplasms/drug therapy , Organosilicon Compounds/chemistry , Phenylalanine/chemistry , Apoptosis , Cell Proliferation , Humans , Metal Nanoparticles/chemistry , Neoplasms/pathology , Tumor Cells, CulturedABSTRACT
Periodic Mesoporous Organosilica Nanoparticles (PMONPs) are nanoparticles of high interest for nanomedicine applications. These nanoparticles are not composed of silica (SiO2). They belong to hybrid organic-inorganic systems. We considered using these nanoparticles for CO2 release as a contrast agent for High Intensity Focused Ultrasounds (HIFU). Three molecules (P1-P3) possessing two to four triethoxysilyl groups were synthesized through click chemistry. These molecules possess a tert-butoxycarbonyl (BOC) group whose cleavage in water at 90-100 °C releases CO2. Bis(triethoxysilyl)ethylene E was mixed with the molecules Pn (or not for P3) at a proportion of 90/10 to 75/25, and the polymerization triggered by the sol-gel procedure led to PMONPs. PMONPs were characterized by different techniques, and nanorods of 200-300 nm were obtained. These nanorods were porous at a proportion of 90/10, but non-porous at 75/25. Alternatively, molecules P3 alone led to mesoporous nanoparticles of 100 nm diameter. The BOC group was stable, but it was cleaved at pH 1 in boiling water. Molecules possessing a BOC group were successfully used for the preparation of nanoparticles for CO2 release. The BOC group was stable and we did not observe release of CO2 under HIFU at lysosomal pH of 5.5. The pH needed to be adjusted to 1 in boiling water to cleave the BOC group. Nevertheless, the concept is interesting for HIFU theranostic agents.
Subject(s)
Nanomedicine , Nanoparticles/chemistry , Organosilicon Compounds/chemistry , Silicon Dioxide/chemistry , Carbon Dioxide/chemistry , Click Chemistry , Contrast Media/chemistry , Drug Carriers/chemistry , Formic Acid Esters/chemistry , Humans , Nanoparticles/therapeutic use , Nanotubes/chemistry , Organosilicon Compounds/therapeutic use , Porosity , Silicon Dioxide/therapeutic useABSTRACT
INTRODUCTION: Research on the volatile oil composition of Thymus kotschyanus Boiss was conducted by applying mesoporous organosilica based on alkylimidazolium ionic liquid (PMO-IL) as a fibre coating material via a method referred to as microwave-assisted headspace solid-phase microextraction (MA-HS-SPME). METHODOLOGY: This technique entails microwave irradiation of the sample and collection of the volatile sample components. These components are further introduced into a gas chromatography-mass spectrometry (GC-MS) injection port for further analysis. A simplex method was used for the optimisation of three different parameters affecting the efficiency of the extraction. CONCLUSION: The MA-HS-SPME method proved to be the most suitable technique in oil determination and extraction from Thymus kotschyanus owing to its advantageous aspects of cost effectiveness, simplicity and solvent independence.
Subject(s)
Imidazoles/chemistry , Ionic Liquids/chemistry , Microwaves , Oils, Volatile/analysis , Silicon Dioxide/chemistry , Solid Phase Microextraction/methods , Thymus Plant/chemistry , Gas Chromatography-Mass Spectrometry/methods , Solvents/chemistryABSTRACT
(1) Background: Nanomedicine has recently emerged as a promising field, particularly for cancer theranostics. In this context, nanoparticles designed for imaging and therapeutic applications are of interest. We, therefore, studied the encapsulation of upconverting nanoparticles in mesoporous organosilica nanoparticles. Indeed, mesoporous organosilica nanoparticles have been shown to be very efficient for drug delivery, and upconverting nanoparticles are interesting for near-infrared and X-ray computed tomography imaging, depending on the matrix used. (2) Methods: Two different upconverting-based nanoparticles were synthesized with Yb3+-Er3+ as the upconverting system and NaYF4 or BaLuF5 as the matrix. The encapsulation of these nanoparticles was studied through the sol-gel procedure with bis(triethoxysilyl)ethylene and bis(triethoxysilyl)ethane in the presence of CTAB. (3) Results: with bis(triethoxysilyl)ethylene, BaLuF5: Yb3+-Er3+, nanoparticles were not encapsulated, but anchored on the surface of the obtained mesoporous nanorods BaLuF5: Yb3+-Er3+@Ethylene. With bis(triethoxysilyl)ethane, BaLuF5: Yb3+-Er3+ and NaYF4: Yb3+-Er3+nanoparticles were encapsulated in the mesoporous cubic structure leading to BaLuF5: Yb3+-Er3+@Ethane and NaYF4: Yb3+-Er3+@Ethane, respectively. (4) Conclusions: upconversion nanoparticles were located on the surface of mesoporous nanorods obtained by hydrolysis polycondensation of bis(triethoxysilyl)ethylene, whereas encapsulation occurred with bis(triethoxysilyl)ethane. The later nanoparticles NaYF4: Yb3+-Er3+@Ethane or BaLuF5: Yb3+-Er3+@Ethane were promising for applications with cancer cell imaging or X-ray-computed tomography respectively.
Subject(s)
Nanoparticles/chemistry , Organosilicon Compounds/chemistry , Drug Delivery Systems/methods , Erbium/chemistry , Ethane/chemistry , Fluorides/chemistry , Hydrolysis , Nanomedicine/methods , Nanotubes/chemistry , Technology, Pharmaceutical/methods , Ytterbium/chemistry , Yttrium/chemistryABSTRACT
The catalytic deoxygenation of bio-based feedstocks to fuels and chemicals presents new challenges to the catalytic scientist, with many transformations either performed in or liberating water as a byproduct during reaction. The design of catalysts with tunable hydrophobicity to aid product and reactant adsorption or desorption, respectively, is vital for processes including (trans)esterification and condensation reactions employed in sustainable biodiesel production and bio-oil upgrading processes. Increasing surface hydrophobicity of catalyst materials offers a means to displace water from the catalyst active site, and minimizes potential deactivation or hydrolysis side reactions. Hybrid organicâ»inorganic porous solids offer exciting opportunities to tune surface polarity and hydrophobicity, as well as critical parameters in controlling adsorption, reactant activation, and product selectivity in liquid and vapor phase catalysis. Here, we review advances in the synthesis and application of sulfonic-acid-functionalized periodic mesoporous organosilicas (PMO) as tunable hydrophobic solid acid catalysts in reactions relevant to biorefining and biofuel production.
Subject(s)
Acids/chemistry , Organically Modified Ceramics/chemistry , Biofuels , Biomass , Catalysis , Hydrolysis , Hydrophobic and Hydrophilic Interactions , PorosityABSTRACT
The properties of materials confined in porous media are important in scientific and technological aspects. Topology, size, and surface polarity of the pores play a critical role in the confinement effects, however, knowledge regarding the guest-pore interface structure is still lacking. Herein, we show that the molecular mobility of water confined in periodic mesoporous organosilicas (PMOs) is influenced by the polarity of the organic moiety. Multidimensional solid-state NMR spectroscopy directly probes the spatial arrangement of water inside the pores, showing that water interacts either with only the silicate layer or with both silicate and organic layers depending on the alternating surface polarity. A modulated and a uniform pore filling mode are proposed for different types of PMOs.
ABSTRACT
The synthesis of mesoporous nanoparticles with controllable structure and organic groups is important for their applications. In this work, yolk-shell-structured periodic mesoporous organosilica (PMO) nanoparticles simultaneously incorporated with ethane-, thioether-, and benzene-bridged moieties are successfully synthesized. The preparation of the triple-hybridized PMOs is via a cetyltrimethylammonium bromide-directed sol-gel process using mixed bridged silsesquioxanes as precursors and a following hydrothermal treatment. The yolk-shell-structured triple-hybridized PMO nanoparticles have large surface area (320 m(2) g(-1) ), ordered mesochannels (2.5 nm), large pore volume (0.59 cm(3) g(-1) ), uniform and controllable diameter (88-380 nm), core size (22-110 nm), and shell thickness (13-45 nm). In vitro cytotoxicity, hemolysis assay, and histological studies demonstrate that the yolk-shell-structured triple-hybridized PMO nanoparticles have excellent biocompatibility. Moreover, the organic groups in the triple-hybridized PMOs endow them with an ability for covalent connection of near-infrared fluorescence dyes, a high hydrophobic drug loading capacity, and a glutathione-responsive drug release property, which make them promising candidates for applications in bioimaging and drug delivery.
Subject(s)
Drug Carriers/chemistry , Nanoparticles/chemistry , Organosilicon Compounds/chemistry , Cetrimonium , Cetrimonium Compounds/chemistry , Drug Liberation , Hydrophobic and Hydrophilic Interactions , Porosity , Surface PropertiesABSTRACT
Periodic mesoporous organosilica (PMO) is a unique material that has a crystal-like wall structure with coordination sites for metal complexes. A Ru complex, [RuCl2 (CO)3 ]2 , is successfully immobilized onto 2,2'-bipyridine (BPy) units of PMO to form a single-site catalyst, which has been confirmed by various physicochemical analyses. Using NaClO as an oxidant, the Ru-immobilized PMO oxidizes the tertiary C-H bonds of adamantane to the corresponding alcohols at 57 times faster than the secondary C-H bonds, thereby exhibiting remarkably high regioselectivity. Moreover, the catalyst converts cis-decalin to cis-9-decalol in a 63 % yield with complete retention of the substrate stereochemistry. The Ru catalyst can be separated by simple filtration and reused without loss of the original activity and selectivity for the oxidation reactions.
ABSTRACT
Periodic mesoporous organosilica (PMO) materials offer a strategy to position molecular semiconductors within a highly defined, porous network. We developed thin films of a new semiconducting zinc phthalocyanine-bridged PMO exhibiting a face-centered orthorhombic pore structure with an average pore diameter of 11â nm. The exceptional degree of order achieved with this PMO enabled us to create thin films consisting of a single porous domain throughout their entire thickness, thus providing maximal accessibility for subsequent incorporation of a complementary phase. The phthalocyanine building blocks inside the pore walls were found to be well-aggregated, enabling electronic conductivity and extending the light-harvesting capabilities to the near IR region. Ordered 3D heterojunctions capable of promoting photo-induced charge transfer were constructed by impregnation of the PMO with a fullerene derivative. When integrated into a photovoltaic device, the infiltrated PMO is capable of producing a high open-circuit voltage and a considerable photocurrent, which represents a significant step towards potential applications of PMOs in optoelectronics.
ABSTRACT
This research focused on utilizing periodic mesoporous organosilica with imidazolium framework (PMO-IL), to immobilize a metagenome-sourced protease (PersiProtease1), thereby enhancing its functional efficiency and catalytic effectiveness in processing primary proteins found in tannery wastewater. The successful immobilization of enzyme was confirmed through the use of N2 adsorption-desorption experiment, XRD, FTIR, TEM, FESEM, EDS and elemental analytical techniques. The immobilized enzyme exhibited greater stability in the presence of various metal ions and inhibitors compared to its free form. Furthermore, enzyme binding to PMO-IL nanoparticles (NPs) reduced leaching, evidenced by only 11.41 % of enzyme leakage following a 120-min incubation at 80 °C and 6.99 % after 240 min at 25 °C. Additionally, PersiPro@PMO-IL maintained impressive operational consistency, preserving 62.24 % of its activity over 20 cycles. It also demonstrated notable stability under saline conditions, with an increase of 1.5 times compared to the free enzyme in the presence of 5 M NaCl. The rate of collagen hydrolysis by the immobilized protease was 46.82 % after a 15-minute incubation at 60 °C and marginally decreased to 39.02 % after 20 cycles indicative of sustained efficacy without significant leaching throughout the cycles. These findings underscore the effectiveness of PMO-IL NPs as a viable candidate for treating wastewater containing protein.
ABSTRACT
A novel palladium-loaded yolk-shell structured nanomaterial with magnetite core and phenylene-based periodic mesoporous organosilica (PMO) shell (Fe3O4@YS-Ph-PMO/Pd) nanocatalyst was synthesized for the reduction of nitrobenzenes. The Fe3O4@YS-Ph-PMO/Pd was prepared through cetyltrimethylammonium bromide (CTAB) directed condensation of 1,4-bis(triethoxysilyl)benzene (BTEB) around Fe3O4@silica nanoparticles followed by treatment with palladium acetate. This nanocatalyst was characterized by using Fourier transform infrared (FT-IR) spectroscopy, thermal gravimetric analysis (TGA), low-angle and wide-angle powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and vibrating sample magnetometer (VSM) analyses. These analyses showed a magnetic nanomaterial with high chemical and thermal stability for the designed composite. The Fe3O4@YS-Ph-PMO/Pd nanocomposite was employed as a powerful and highly recoverable catalyst in the green reduction of nitroarenes in H2O at room temperature. A variety of nitroarene derivatives were applied as substrate in the presence of 0.9 mol% of Fe3O4@YS-Ph-PMO/Pd catalyst. All nitroarenes were selectively converted to their corresponding amines with high to excellent yields (92-96%) within short reaction times (10-18 min). This catalyst was recovered and reused at least 11 times without significant decrease in efficiency and stability.
ABSTRACT
BACKGROUND: Attentions regarding ordered mesoporous silica materials (OMSs), with large specific surface areas and narrow pore size distribution, which are prepared via self-assembly techniques, have been raised in sorption, separation, and sample preparation. However, in order to extend and improve their applications, a functionalization step is required. Organic units can be anchored on the inner or outer surface as well as in the silica wall framework by co-condensation-, grafting-, and periodic mesoporous organosilica (PMO) preparation approaches. Apparently, by synthesizing PMO with extensive and flexible organic bridging groups within the mesoporous wall, an efficient extractive phase can be achieved. RESULTS: We employed tyrosine amino acid to synthesize a PMO-based extractive phase. The FT-IR, 1H NMR, HR-ESI-MS, Low angle-XRD, TEM, FESEM, BET, and EDX-MAP analyses confirmed the successful synthesis of PMO within the salt-assisted templating method. A comprehensive study on sorption behavior of PMO was performed and its efficiency was evaluated against the grafting and co-condensation methods. Then, it was implemented to the pipette tip-micro solid phase extraction (PT-µ-SPE) of widely used non-steroidal anti-inflammatory drugs (NSAIDs) in water/wastewaters. Limits of detection and quantification were obtained in the range of 0.1-1.5 and 0.3-5 µg L-1, respectively. The calibration plots are linear in the 1-1000, 3-1000, 10-750, and 3-750 µg L-1, respectively. The intra-and inter-day precision at 50 and 200 µg L-1 levels are 2.9-7.1 % and 3.5-8%, while recoveries are between 84 and 111 %. SIGNIFICANCE: High-capacity tyrosine functionalized PMO with 2D hexagonal symmetry silica mesoporous structures found to be highly efficient extractive media. Despite the bulkiness and flexibility of the bridging group within the mesoporous wall, the synthesis condition was optimized in order to load more organic content in the PMO structure. The PMO performance was superior over organically modified ordered mesoporous silica materials prepared by the grafting and co-condensation methods.
Subject(s)
Amino Acids , Tyrosine , Spectroscopy, Fourier Transform Infrared , Anti-Inflammatory Agents, Non-Steroidal , Silicon DioxideABSTRACT
The preparation of yolk-shell structured magnetic mesoporous composites is a significant subject between researchers. Especially, modification of theses composites with ionic liquid/metal complex is very important for catalytic processes. In the present study, a novel magnetic methylene-based periodic mesoporous organosilica (PMO)-supported ionic liquid/Cu complex with yolk-shell structure (YS-Fe3O4@PMO/IL-Cu) was prepared via the soft template-assisted method. The TGA, FT-IR, SEM, EDX, XRD, VSM, nitrogen-sorption, and ICP techniques were employed to identify YS-Fe3O4@PMO/IL-Cu. The YS-Fe3O4@PMO/IL-Cu material was applied as a powerful nanocatalyst for the synthesis of pyranopyrazoles under ultrasonic media. The study demonstrated that the YS-Fe3O4@PMO/IL-Cu nanocatalyst is highly recyclable, selective, and effective. The leaching test was performed to investigate the nature of the designed catalyst under the applied conditions.
ABSTRACT
In this work, we have proposed a strategy to fabricate double-shell nanotubes as amphiphilic photoactive nanoreactors (HTTBPC) through the ordered hybridization of mesoporous organosilicon (PMO) and titanium dioxide (TiO2) nanotubes. Unlike the previous rough composite, the heterogeneous structure established between cobalt-porphyrin functionalized PMO and conventional TiO2 has a staggered matching band gap, which makes it have excellent light harvesting and high carrier separation ability. This is still unexplored. Interestingly, the prepared photocatalysts exhibited superior activity (99%) and benzaldehyde selectivity (94%) in the oxidation of styrene in water at room temperature, which was 3.8 and 2.8 times higher than that of TiO2 nanotubes and PMO functionalized with cobalt porphyrin, respectively. It was demonstrated that the strong interaction between cobalt porphyrin PMO and TiO2 improved the separation of photogenerated carriers and the amphiphilic properties of mesoporous organosilica boosted the adsorption of substrate molecules in water, contributing to the significantly enhanced photocatalytic activity. This work provides a design of high-performance photocatalysts for alkene oxidation under green conditions.